CN1466568A - Preparation of hydroxyalkylcarbamates from six-membered cyclic carbonates - Google Patents
Preparation of hydroxyalkylcarbamates from six-membered cyclic carbonates Download PDFInfo
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- CN1466568A CN1466568A CNA018161987A CN01816198A CN1466568A CN 1466568 A CN1466568 A CN 1466568A CN A018161987 A CNA018161987 A CN A018161987A CN 01816198 A CN01816198 A CN 01816198A CN 1466568 A CN1466568 A CN 1466568A
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- hydrogen
- cyclic carbonate
- hydroxyalkyl carbamate
- respectively independently
- composition
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- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract 19
- 238000002360 preparation method Methods 0.000 title description 17
- 238000000034 method Methods 0.000 claims abstract description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000008199 coating composition Substances 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 14
- -1 hydroxyalkyl carbamate Chemical compound 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical class CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- CYHGVTHKNRESIV-UHFFFAOYSA-N (3-hydroxy-2-methylpropyl) carbamate Chemical compound OCC(C)COC(N)=O CYHGVTHKNRESIV-UHFFFAOYSA-N 0.000 description 1
- YQLCYVREFJVRBW-UHFFFAOYSA-N 3-hydroxybutyl carbamate Chemical compound CC(O)CCOC(N)=O YQLCYVREFJVRBW-UHFFFAOYSA-N 0.000 description 1
- BSBQJOWZSCCENI-UHFFFAOYSA-N 3-hydroxypropyl carbamate Chemical compound NC(=O)OCCCO BSBQJOWZSCCENI-UHFFFAOYSA-N 0.000 description 1
- XTXMKSJDRKQMHQ-UHFFFAOYSA-N 4-hydroxybutan-2-yl carbamate Chemical compound OCCC(C)OC(N)=O XTXMKSJDRKQMHQ-UHFFFAOYSA-N 0.000 description 1
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical class CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
Abstract
A method of preparing hydroxyalkylcarbamates from six-membered cyclic carbonates. The method involves reacting a six-membered cyclic carbonate with anhydrous ammonia or aqueous ammonium hydroxide. The present invention also provides for hydroxyalkylcarbamates prepared from six-membered cyclic carbonates, and for coating compositions comprising hydroxyalkylcarbamates prepared according to the present invention.
Description
Technical field
The present invention relates to carbamate, specifically, is the hydroxyalkyl carbamate by six-ring carbonic ether preparation, and prepares the method for this hydroxyalkyl carbamate and contain coating composition according to the hydroxyalkyl carbamate of the present invention's preparation.
Background of invention
The derivative of carbamate serves many purposes, including, but not limited to, be used for the synthetic of agricultural chemicals, sterilant, antibiotic and urethane.Derivative by carbamate, be specially hydroxyalkyl carbamate, the urethane of preparation can be used for comprising in the multiple application of various coating technologies, as Marvin L.Green in 1-3 day in March, 2000 at New Orleans, Louisiana (New Orleans, it is such that " the low VOC carbamate functional based coating composition that is used for automobile finish " introduced in the international water-based of LA) holding, high solid and the powder coating symposial further discussed, and this article is introduced the present invention as a reference.
Making the interested especially automobile varnish coating of people technology is to have utilized recent business-like hydroxypropyl carbamate (HPC) compound, and this compound is normally prepared by five-membered ring carbonate ester.But the purifying of this HPC compound is complicated owing to adopt competitive reversed reaction.Specifically, when purifying (just removing excess ammonia), this HPC compound trends towards reversing gets back to its starting raw material.Therefore, if inappropriate processing, these HPC compounds can be easy to contaminated.
With different, by the easy purifying of carbamate of six-ring carbonic ether preparation by the carbamate of five-membered ring carbonate ester preparation.Specifically, in purifying (promptly removing excess ammonia) process, the carbamate that is prepared by the six-ring carbonic ether can not reverse the starting raw material of getting back to them.It is reported that this stability is because the six-ring carbonic ether has bigger ring strained cause with respect to pentacyclic counterpart.Therefore, the hydroxyalkyl carbamate by the preparation of six-ring carbonic ether has more superior handling property than the hydroxyalkyl carbamate by the five-membered ring carbonate ester preparation.
Summary of the invention
Therefore, in one embodiment, the present invention relates to a kind of method for preparing hydroxyalkyl carbamate by the six-ring carbonic ether.Hydroxyalkyl carbamate of the present invention can prepare by six-ring carbonic ether and anhydrous ammonia are reacted.This preparation can be expressed from the next:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one respectively independently to about six carbon atom straight or branched alkyl.Hydroxyalkyl carbamate of the present invention also can prepare by six-ring carbonic ether and ammonium hydroxide aqueous solution are reacted, and this preparation can be represented by following formula:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.
In another embodiment, the invention provides hydroxyalkyl carbamate by the preparation of six-ring carbonic ether.Hydroxyalkyl carbamate of the present invention has following structure:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.
In yet another embodiment, the invention provides the coating composition that contains according to the hydroxyalkyl carbamate of the present invention's preparation.
Detailed description of the preferred embodiments
The invention provides the method for preparing hydroxyalkyl carbamate by the six-ring carbonic ether.According to method of the present invention, hydroxyalkyl carbamate can prepare by making six-ring carbonic ether and anhydrous ammonia or reacting with ammonium hydroxide aqueous solution.
According to method of the present invention, hydroxyalkyl carbamate can be by preparing in the reactor that a kind of six-ring carbonic ether with following structure is packed into.
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.Preferably, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.More preferably, R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.Behind reaction vessel that the six-ring carbonic ether is packed into,,, purged at least 30 minutes such as (but being not limited to) nitrogen with this container rare gas element.Then, with about 1.10 normal anhydrous ammonias this reaction vessel is pressurized to about 50psig between about 1000psig; Be preferably about 50psig between about 300psig; More preferably about 100psig is between about 250psig.Add after the anhydrous ammonia, reactor should should be heated to the temperature between about 25 ℃ to about 100 ℃; Be preferably between about 45 ℃ to about 75 ℃; More preferably about 55 ℃, and keep at least about two hours.Carry out to observe the reduction of ammonia pressure in the process in reaction.After the heating, with being about to reaction product cooling and purifying.Should remove the unreacted ammonia of any trace, the preferred vacuum of about 3torr of utilizing is carried out.This method can be represented with following formula:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.Preferably, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.More preferably, R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.
In addition, according to other method of the present invention, hydroxyalkyl carbamate can prepare by at first tetrahydrofuran (THF) (THF) and six-ring carbonic ether with following structure being mixed in reactor:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.Preferably, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.More preferably, R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.After the mixing, this container rare gas element such as (but being not limited to) nitrogen, should be purged 30 minutes at least.Behind the purging, ammonium hydroxide aqueous solution is joined lentamente in the solution of this carbonic ether/THF (under barometric point).After adding ammonium hydroxide, should be with the mixture heating up that obtains to about 60 ℃, and kept about two hours.Then, THF, water and the evaporation of excessive hydrogen ammonium oxide are waved.This method can be represented with following formula:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.Preferably, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.More preferably, R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.
The present invention also provides the hydroxyalkyl carbamate by the preparation of six-ring carbonic ether.As top disclosed, hydroxyalkyl carbamate of the present invention can prepare by six-ring carbonic ether and anhydrous ammonia or ammonium hydroxide aqueous solution are reacted, wherein the six-ring carbonic ether has following structure:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.Preferably, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.More preferably, R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.The available following formula of the preparation of hydroxyalkyl carbamate of the present invention is represented:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.Preferably, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.More preferably, R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.
Hydroxyalkyl carbamate of the present invention can be used to prepare coating composition by any appropriate means well-known to those skilled in the art.Preferably, hydroxyalkyl carbamate of the present invention can prepare coating composition according to U.S. Patent No. 5605965 described methods, and this patent is introduced the present invention as a reference.Usually, described coating composition can react under suitable condition by making hydroxyalkyl carbamate of the present invention, produces the polymkeric substance with at least one carbamate-functional and prepares.Subsequently, can with this polymkeric substance with contain a plurality of can with the compound of the functional group of carbamate groups reaction.This reaction mixture can be chosen wantonly and solvent.Can choose wantonly and promote curing reaction with catalyzer.
Coating composition of the present invention can adopt arbitrary technology known in the art to apply object.These technology comprise, for example spraying, dip-coating, roller coat, curtain coating and similar approach.For the automobile body plate, spraying is preferred.
Preferably make coating composition of the present invention stand to promote the Conditioning of coating curing.Although can adopt various curings, preferably be heating and curing.
The following examples are used for describing the present invention, do not plan to limit the scope of the invention by any way.
Embodiment 1
The 100.0 gram 5-methyl isophthalic acids of in the autoclave of a 300ml, packing into, 3-diox-2-ketone (being that by diethyl carbonate and 2-methyl isophthalic acid, 3 one propylene glycol prepared in reaction form under the condition that salt of wormwood exists), and with nitrogen purging 30 minutes.Subsequently, with 16.1 gram anhydrous ammonias (1.10 equivalent) this autoclave is forced into 200psig, and is heated to 55 ℃ temperature, the pressure of ammonia begins to drop to 140psig in the meantime.Mixture was kept 2.5 hours down at 55 ℃, then cooling.After being cooled to 45 ℃, the pressure of autoclave is 132psig.Resulting product is the yellow liquid of viscosity, in a rotary evaporator, under 3torr, this product liquid is heated to 45 ℃ to remove the unreacted ammonia of trace subsequently.Resulting product is really known by LC and LC/MS is 2-methyl-3-hydroxypropyl carbamate (94.5%) and 2-methyl isophthalic acid, ammediol (5.0%).
Embodiment 2
The 100.0 gram 4-methyl isophthalic acids of in the autoclave of a 300ml, packing into, 3-diox-2-ketone (be under the condition that salt of wormwood exists, form) by diethyl carbonate and 1,3 butylene glycol prepared in reaction, and with nitrogen purging 30 minutes.Subsequently, with 16.1 gram anhydrous ammonias (1.10 equivalent) autoclave is forced into 195psig, and is heated to 55 ℃ temperature, the pressure of ammonia begins to drop to 105psig in the meantime.Mixture was kept 2.5 hours down at 55 ℃, then cooling.After being cooled to 45 ℃, the pressure of autoclave is 101psig.Resulting product is the yellow liquid of viscosity, in a rotary evaporator, under 3torr, this product liquid is heated to 45 ℃ to remove the unreacted ammonia of trace subsequently.Resulting product is really known for being two kinds of mixture of isomers, i.e. 1-methyl-3-hydroxypropyl carbamate (49.2%) and 3-methyl-3-hydroxypropyl carbamate (46.6%), and a spot of 1,3 butylene glycol (2.5%) by LC and LC/MS.
Embodiment 3
With 83.7 gram (0.721mol) 5-methyl isophthalic acids, 3-diox-2-ketone adds in one one liter the round-bottomed flask, and this flask is equipped with dropping funnel, thermocouple probe, magnetic stirring bar.THF with 100ml dilutes carbonic ether subsequently.Then, 91.22 gram (0.764mol) ammonium hydroxide (29wt%) aqueous solution are added in the dropping funnel.This system, slowly is added to solution of ammonium hydroxide in carbonic ether/THF solution after about 30 minutes with nitrogen purging.Can be observed exothermic heat of reaction (about 47 ℃).After all ammonium hydroxide being joined in this carbonic ether/THF mixture, resulting mixture was heated under about 60 ℃ temperature about two hours.After the cooling, resulting mixture in rotary evaporator, is heated to 45 ℃ under 3torr, anhydrates to remove, THF and excessive ammonium hydroxide.Resulting product is water white product liquid (72.3 gram).LC/MS and LC analyze and determine that this product contains 92.8%2-methyl-3-hydroxypropyl carbamate and 6.9%2-methyl isophthalic acid, ammediol.
Embodiment 4a (expection)
The hydroxyalkyl carbamate of embodiment 1 preparation reacts subsequently under suitable condition to produce a kind of polymkeric substance with at least one carbamate-functional.Subsequently with this polymkeric substance and contain a plurality of can with the compound of the functional group of carbamate groups reaction.Can choose wantonly this reaction mixture and solvent.Can choose wantonly with catalyzer and promote this curing reaction.
Embodiment 4b (expection)
The hydroxyalkyl carbamate of embodiment 2 preparations reacts subsequently under suitable condition to produce a kind of polymkeric substance with at least one carbamate-functional.Subsequently with this polymkeric substance and contain a plurality of can with the compound of the functional group of carbamate groups reaction.Can choose wantonly this reaction mixture and solvent.Can choose wantonly with catalyzer and promote this curing reaction.
Embodiment 4c (expection)
The hydroxyalkyl carbamate of embodiment 3 preparations reacts subsequently under suitable condition to produce a kind of polymkeric substance with at least one carbamate-functional.Subsequently with this polymkeric substance and contain a plurality of can with the compound of the functional group of carbamate groups reaction.Can choose wantonly this reaction mixture and solvent.Can choose wantonly with catalyzer and promote this curing reaction.
Embodiment 5 (expection)
The coating composition for preparing in embodiment 4a, 4b and 4c is sprayed onto on the steel plate that had sprayed priming paint and deburring in advance.With this steel plate oven dry.Subsequently this steel plate is placed under the natural climate condition, this steel plate demonstrates the environmental attack effect that obviously reduces than the steel plate with traditional varnish coating.
Although provided and described these illustrative embodiments, above open in, it all is possible improving on a large scale, changing and substitute.In some cases, some feature of disclosed embodiment can be used under the situation of not using corresponding further feature.Therefore, in a wide range and with the corresponding to mode of scope of the present invention explain additional claims be suitable.
Claims (34)
1. hydroxyalkyl carbamate composition by anhydrous ammonia or ammonium hydroxide aqueous solution and cyclic carbonate prepared in reaction, wherein cyclic carbonate has following structure:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.
2. the hydroxyalkyl carbamate composition of claim 1, wherein anhydrous ammonia and cyclic carbonate are to react between about 25 ℃ to about 100 ℃ in temperature.
3. the hydroxyalkyl carbamate composition of claim 1, wherein anhydrous ammonia and cyclic carbonate react between about 1000psig for about 50psig at pressure.
4. the hydroxyalkyl carbamate composition of claim 1, wherein anhydrous ammonia and cyclic carbonate are to react between about 45 ℃ to about 75 ℃ in temperature.
5. the hydroxyalkyl carbamate composition of claim 1, wherein anhydrous ammonia and cyclic carbonate react between about 300psig for about 50psig at pressure.
6. the hydroxyalkyl carbamate composition of claim 1, wherein R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.
7. the hydroxyalkyl carbamate composition of claim 1, wherein R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.
8. the hydroxyalkyl carbamate composition of claim 1, wherein ammonium hydroxide aqueous solution and cyclic carbonate react under barometric point.
9. one kind prepares the hydroxyalkyl carbamate method for compositions, and this method comprises the step that makes anhydrous ammonia and cyclic carbonate reaction, and wherein said cyclic carbonate has following structure:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.
10. the method for claim 9, wherein reactions steps is to carry out between about 25 ℃ to about 100 ℃ in temperature.
11. the method for claim 9, wherein reactions steps is carried out between about 1000psig for about 50psig at pressure.
12. the method for claim 9 further comprises the step of the described hydroxyalkyl carbamate composition of purifying.
13. the method for claim 12, wherein said purification step is undertaken by vacuum.
14. the method for claim 9, wherein R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.
15. the method for claim 9, wherein R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.
16. one kind prepares the hydroxyalkyl carbamate method for compositions, this method comprises the step that makes anhydrous ammonia and cyclic carbonate reaction, and wherein said cyclic carbonate has following structure:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently, and react wherein that pressure carries out between about 1000psig for about 50psig between temperature is for about 25 ℃ to about 100 ℃ to about six carbon atom.
17. the method for claim 16 further comprises the step of the described hydroxyalkyl carbamate composition of purifying.
18. the method for claim 17, wherein said purification step is undertaken by vacuum.
19. the method for claim 16, wherein said reactions steps are to carry out between about 45 ℃ to about 75 ℃ in temperature.
20. the method for claim 16, wherein said reactions steps is carried out between about 300psig for about 50psig at pressure.
21. the method for claim 16, wherein R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.
22. the method for claim 16, wherein R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.
23. one kind prepares the hydroxyalkyl carbamate method for compositions, this method comprises the step that makes ammonium hydroxide aqueous solution and cyclic carbonate reaction, and wherein cyclic carbonate has following structure:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom.
24. the method for claim 23, wherein said reactions steps is carried out under barometric point.
25. the method for claim 23 further comprises the step of purifying hydroxyalkyl carbamate composition.
26. the method for claim 25, wherein purification step is undertaken by evaporation.
27. the method for claim 23, wherein R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.
28. the method for claim 23, wherein R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.
29. a coating composition comprises:
A. polymkeric substance with at least one carbamate-functional, wherein this polymkeric substance is that reaction product hydroxyalkyl carbamate by anhydrous ammonia or ammonium hydroxide aqueous solution and a kind of cyclic carbonate is prepared from, and wherein cyclic carbonate has following structure:
R wherein
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one straight or branched alkyl respectively independently to about six carbon atom, and
B. one kind has the composition a plurality of and functional group that carbamate-functional reacts.
30. the coating composition of claim 29 further comprises a kind of solvent.
31. the coating composition of claim 29 further comprises a kind of catalyzer.
32. the coating composition of claim 30 further comprises a kind of catalyzer.
33. the coating composition of claim 29, wherein R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or have about one alkyl respectively independently to about two carbon atoms.
34. the coating composition of claim 29, wherein R
1-R
6In at least four substituting groups be hydrogen, and R
1-R
6In at least one substituting group be methyl or ethyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/669,220 | 2000-09-25 | ||
| US09/669,220 US6262297B1 (en) | 2000-09-25 | 2000-09-25 | Preparation of hydroxyalkylcarbamates from six-membered cyclic carbonates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1466568A true CN1466568A (en) | 2004-01-07 |
Family
ID=24685558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA018161987A Pending CN1466568A (en) | 2000-09-25 | 2001-05-18 | Preparation of hydroxyalkylcarbamates from six-membered cyclic carbonates |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US6262297B1 (en) |
| EP (1) | EP1320519A1 (en) |
| JP (1) | JP2004509944A (en) |
| KR (1) | KR20030040489A (en) |
| CN (1) | CN1466568A (en) |
| AU (1) | AU2001263245A1 (en) |
| TW (1) | TW553924B (en) |
| WO (1) | WO2002026700A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1980983B (en) * | 2004-06-18 | 2010-05-05 | 科聚亚公司 | Polymers and their use as coatings |
| CN115403765A (en) * | 2022-10-05 | 2022-11-29 | 大连理工大学 | Chemically recyclable high-strength non-isocyanate polyurethane and preparation method thereof |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6624279B2 (en) * | 1999-05-21 | 2003-09-23 | Basf Corporation | Water-soluble carbamate materials |
| US6624241B2 (en) | 1999-05-21 | 2003-09-23 | Basf Corporation | Waterborne coating compositions containing materials dispersed with water-soluble carbamate materials |
| DE10004498A1 (en) * | 2000-02-02 | 2001-08-09 | Basf Coatings Ag | New diethyloctandiol dicarbamate and diethyloctandiol diallophanate positional isomers are used for vehicle and electronic parts |
| US6838530B2 (en) * | 2001-11-29 | 2005-01-04 | Basf Corporation | Method of preparing various multifunctional materials using limited starting reactants |
| US20040030176A1 (en) * | 2001-09-05 | 2004-02-12 | Ohrbom Walter H. | Gamma hydroxy carbamate compounds and method of making and using the same |
| US6900270B2 (en) | 2002-10-31 | 2005-05-31 | Basf Corporation | Curable coating compositions with carbamate compounds |
| US6825286B2 (en) * | 2001-11-29 | 2004-11-30 | Basf Corporation | Method for determining the water solubility or water dispersibility of waterborne beta-hydroxy primary carbamate functional graft materials |
| US6977309B2 (en) | 2002-10-31 | 2005-12-20 | Basf Corporation | Compounds having a secondary or tertiary hydroxy of halide group separated from a primary carbamate group by three or more carbon atoms and a method of making the same |
| US6858674B2 (en) | 2002-10-31 | 2005-02-22 | Basf Corporation | Carbamate functional materials, a method of making said materials, and curable coating compositions containing said materials |
| AU2003221909A1 (en) * | 2002-04-16 | 2003-11-03 | Huntsman Petrochemical Corporation | 6-membered cyclic carbonates |
| US7232863B2 (en) | 2002-10-31 | 2007-06-19 | Basf Corporation | Functional addition polymers and a method for their preparation |
| US20040087728A1 (en) * | 2002-10-31 | 2004-05-06 | Donald Campbell | Carbamate functional addition polymers and a method for their preparation |
| US6890994B2 (en) * | 2002-10-31 | 2005-05-10 | Basf Corporation | Curable coating compositions with carbamate-containing acrylic polymers |
| US20090105498A1 (en) * | 2007-10-18 | 2009-04-23 | Porstmann Frank | Improved process for preparing 2-(substituted phenyol)-2-hydroxy-ethyl-carbamates |
| KR101040613B1 (en) * | 2010-03-04 | 2011-06-10 | 주식회사 미주테크 | Compression device for waste basket |
| US9487662B1 (en) * | 2014-01-21 | 2016-11-08 | Nanotech Industries, Inc. | Radiation-curable biobased flooring compositions with nonreactive additives |
| US11124693B2 (en) * | 2017-02-28 | 2021-09-21 | Indorama Ventures Oxides Llc | Hydroxyalkylurethane kinetic hydrate inhibitors |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2656378A (en) * | 1952-01-04 | 1953-10-20 | Carter Prod Inc | 2, 2-diphenyl-1, 3-propanediol monocarbamate |
| GB873908A (en) * | 1957-04-24 | 1961-08-02 | Carter Prod Inc | Improvements in or relating to 2-methyl-2-úe-propyl-n-monosubstituted-1:3-propanediol dicarbamates and method of manufacture |
| US2937119A (en) * | 1959-06-11 | 1960-05-17 | Carter Prod Inc | Nu-monosubstituted-2, 2-dialkyl-1, 3-propanediol dicarbamates |
| US4758632A (en) | 1984-02-17 | 1988-07-19 | American Cyanamid Company | Self-cross-linkable acrylic polymer containing hydroxyalkyl carbamate groups and coating compositions containing the same |
| US4897435A (en) | 1984-02-17 | 1990-01-30 | American Cyanamid Company | Water based hydroxyalkyl carbamate-containing resins and method of making the same |
| US4484994A (en) * | 1984-02-17 | 1984-11-27 | American Cyanamid Company | Hydroxyalkyl carbamate-containing resins for cathodic electrodeposition and method of making the same |
| US4520167A (en) | 1984-02-17 | 1985-05-28 | American Cyanamid Co. | Hydroxyalkyl carbamate diluent for coating compositions and compositions containing the same |
| US5089617A (en) | 1986-05-16 | 1992-02-18 | American Cyanamid Company | Beta-hydroxyalkylcarbamyl-methylated aminotriazines |
| US4820830A (en) | 1987-03-02 | 1989-04-11 | King Industries, Inc. | Certain hydroxyalkyl carbamates, polymers and uses thereof |
| US5134205A (en) | 1987-03-02 | 1992-07-28 | King Industries | Certain hydroxyalkyl carbamate compounds, homopolymers and copolymers thereof and uses thereof |
| US4883854A (en) | 1988-09-30 | 1989-11-28 | Medtronic, Inc. | Hydroxyl functional monomers |
| US5102923A (en) | 1991-01-14 | 1992-04-07 | American Cyanamid Company | Rigid polyurethane and polyisocyanurate foams |
| US5605965A (en) | 1992-10-23 | 1997-02-25 | Basf Corporation | High gloss and/or high DOI coating utilizing carbamate-functional polymer composition |
| US6020499A (en) | 1997-06-11 | 2000-02-01 | E. I. Du Pont Nemours And Company | Cyclic carbonates and their reactions with amines |
-
2000
- 2000-09-25 US US09/669,220 patent/US6262297B1/en not_active Expired - Fee Related
-
2001
- 2001-05-18 AU AU2001263245A patent/AU2001263245A1/en not_active Abandoned
- 2001-05-18 EP EP01937519A patent/EP1320519A1/en not_active Withdrawn
- 2001-05-18 KR KR10-2003-7004238A patent/KR20030040489A/en not_active Application Discontinuation
- 2001-05-18 JP JP2002531086A patent/JP2004509944A/en active Pending
- 2001-05-18 CN CNA018161987A patent/CN1466568A/en active Pending
- 2001-05-18 WO PCT/US2001/016053 patent/WO2002026700A1/en not_active Application Discontinuation
- 2001-05-23 US US09/863,558 patent/US6710203B2/en not_active Expired - Fee Related
- 2001-06-14 TW TW090114432A patent/TW553924B/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1980983B (en) * | 2004-06-18 | 2010-05-05 | 科聚亚公司 | Polymers and their use as coatings |
| CN115403765A (en) * | 2022-10-05 | 2022-11-29 | 大连理工大学 | Chemically recyclable high-strength non-isocyanate polyurethane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20020040160A1 (en) | 2002-04-04 |
| AU2001263245A1 (en) | 2002-04-08 |
| US6262297B1 (en) | 2001-07-17 |
| EP1320519A1 (en) | 2003-06-25 |
| JP2004509944A (en) | 2004-04-02 |
| US6710203B2 (en) | 2004-03-23 |
| KR20030040489A (en) | 2003-05-22 |
| WO2002026700A1 (en) | 2002-04-04 |
| TW553924B (en) | 2003-09-21 |
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